The present invention relates to 3-(heterocyclyl)benzoylpyrazole derivatives of the formula I 
where:
X is O, NH or N(C1-C6-alkyl);
R1 is nitro, halogen, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, C1-C4-haloalkylthio, C1-C4-alkylsulfonyl or C1-C4-haloalkylsulfonyl;
R2,R3,R4,R5 are hydrogen, C1-C4-alkyl or C1-C4-haloalkyl;
R6 is halogen, nitro, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, C1-C4-haloalkylthio, C1-C4-alkylsulfonyl or C1-C4-haloalkylsulfonyl;
R7 is hydroxyl, C1-C6-alkoxy, C3-C6-alkenyloxy, C1-C6-alkylsulfonyloxy, C1-C6-alkylcarbonyloxy, C1-C4-(alkylthio)carbonyloxy, phenylsulfonyloxy or phenylcarbonyloxy, where the phenyl radical of the two last-mentioned substituents may be partially or fully halogenated and/or may carry one to three of the following groups: nitro, cyano, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy or C1-C4-haloalkoxy;
R8,R9 are C1-C4-alkyl;
R10 is hydrogen or C1-C4-alkyl; where the number of the carbon atoms of the radicals R8,R9 and R10 together is at most 7,
R11 is hydrogen or C1-C4-alkyl;
and its agriculturally useful salts.
Moreover, the invention relates to processes for preparing compounds of the formula I, to compositions comprising them and to the use of these derivatives or of the compositions comprising them for controlling harmful plants.
Pyrazol-4-yl benzoyl derivatives are disclosed in the literature, for example in WO 96/26206 and WO 98/31681.
However, the herbicidal properties of the prior-art compounds and their compatibility with crop plants are not entirely satisfactory. It is an object of the present invention to provide novel, in particular herbicidally active, compounds having improved properties.
We have found that this object is achieved by the 3-(heterocyclyl)benzoylpyrazole derivatives of the formula I and their herbicidal action.
Furthermore, we have found herbicidal compositions which comprise the compounds I and have very good herbicidal action. Moreover, we have found processes for preparing these compositions and methods for controlling undesirable vegetation using the compounds I.
Depending on the substitution pattern, the compounds of the formula I may contain one or more chiral centers, in which case they are present as enantiomers or mixtures of diastereomers. The invention provides both the pure enantiomers or diastereomers and their mixtures.
The compounds of the formula I can also be present in the form of their agriculturally useful salts, the kind of salt usually being immaterial. In general, the salts of those cations or the acid addition salts of those acids are suitable whose cations and anions, respectively, do not adversely affect the herbicidal action of the compounds I.
Suitable cations are, in particular, ions of the alkali metals, preferably lithium, sodium and potassium, of the alkaline earth metals, preferably calcium and magnesium, and of the transition metals, preferably manganese, copper, zinc and iron, and also ammonium, where, if desired, one to four hydrogen atoms may be replaced here by C1-C4-alkyl, hydroxy-C1-C4-alkyl, C1-C4-alkoxy-C1-C4-alkyl, hydroxy-C1-C4-alkoxy-C1-C4-alkyl, phenyl or benzyl, preferably ammonium, dimethylammonium, diisopropylammonium, tetramethylammonium, tetrabutylammonium, 2-(2-hydroxyeth-1-oxy)eth-1-ylammonium, di(2-hydroxyeth-1-yl)ammonium, trimethylbenzylammonium, furthermore phosphonium ions, sulfonium ions, preferably tri(C1-C4-alkyl)sulfonium, and sulfoxonium ions, preferably tri(C1-C4-alkyl)sulfoxonium.
Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, nitrate, bicarbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate and the anions of C1-C4-alkanoic acids, preferably formate, acetate, propionate and butyrate.
The organic molecular moieties mentioned for the substituents R1-R11 or as radicals on phenyl rings are collective terms for individual enumerations of the individual group members. All hydrocarbon chains, i.e. all alkyl, alkylcarbonyl, haloalkyl, alkoxy, haloalkoxy, alkylcarbonyloxy, (alkylthio)carbonyloxy, alkylsulfonyloxy, alkylthio, haloalkylthio, alkylsulfonyl, haloalkylsulfonyl, alkenyl and alkenyloxy moieties can be straight-chain or branched. Unless indicated otherwise, halogenated substituents preferably carry one to five identical or different halogen atoms. The term xe2x80x9chalogenxe2x80x9d represents in each case fluorine, chlorine, bromine or iodine.
Examples of other meanings are:
C1-C4-alkyl, and the alkyl moieties of C1-C4-alkylcarbonyl and C1-C4-alkylcarbonyloxy: for example methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl and 1,1-dimethylethyl;
C1-C6-alkyl, and the alkyl moieties of C1-C6-alkylcarbonyl and C1-C6-alkylcarbonyloxy: C1-C4-alkyl as mentioned above, and also, for example, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1-ethyl-1-methylpropyl and 1-ethyl-3-methylpropyl;
C1-C4-haloalkyl: a C1-C4-alkyl radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, i.e., for example, chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, bromomethyl, iodomethyl, 1-fluoroethyl, 1-chloroethyl, 1-bromoethyl, 1-iodoethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl, 2-fluoropropyl, 3-fluoropropyl, 2,2-difluoropropyl, 2,3-difluoropropyl, 2-chloropropyl, 3-chloropropyl, 2,3-dichloropropyl, 2-bromopropyl, 3-bromopropyl, 3,3,3-trifluoropropyl, 3,3,3-trichloropropyl, 2,2,3,3,3-pentafluoropropyl, heptafluoropropyl, 1-(fluoromethyl)-2-fluoroethyl, 1-(chloromethyl)-2-chloroethyl, 1-(bromomethyl)-2-bromoethyl, 4-fluorobutyl, 4-chlorobutyl, 4-bromobutyl and nonafluorobutyl;
C1-C4-alkoxy: for example methoxy, ethoxy, propoxy, 1-methylethoxy, butoxy, 1-methylpropoxy, 2-methylpropoxy and 1,1-dimethylethoxy;
C1-C6-alkoxy: C1-C4-alkoxy as mentioned above, and also, for example, pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 1,1-dimethylpropoxy, 1,2-dimethylpropoxy, 2,2-dimethylpropoxy, 1-ethylpropoxy, hexoxy, 1-methylpentoxy, 2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, 1,1-dimethylbutoxy, 1,2-dimethylbutoxy, 1,3-dimethylbutoxy, 2,2-dimethylbutoxy, 2,3-dimethylbutoxy, 3,3-dimethylbutoxy, 1-ethylbutoxy, 2-ethylbutoxy, 1,1,2-trimethylpropoxy, 1,2,2-trimethylpropoxy, 1-ethyl-1-methylpropoxy and 1-ethyl-2-methylpropoxy;
C1-C4-haloalkoxy: a C1-C4-alkoxy radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, i.e., for example, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorodifluoromethoxy, bromodifluoromethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2-bromomethoxy, 2-iodoethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2-trichloroethoxy, pentafluoroethoxy, 2-fluoropropoxy, 3-fluoropropoxy, 2-chloropropoxy, 3-chloropropoxy, 2-bromopropoxy, 3-bromopropoxy, 2,2-difluoropropoxy, 2,3-difluoropropoxy, 2,3-dichloropropoxy, 3,3,3-trifluoropropoxy, 3,3,3-trichloropropoxy, 2,2,3,3,3-pentafluoropropoxy, heptafluoropropoxy, 1-(fluoromethyl)-2-fluoroethoxy, 1-(chloromethyl)-2-chloroethoxy, 1-(bromomethyl)-2-bromoethoxy, 4-fluorobutoxy, 4-chlorobutoxy, 4-bromobutoxy and nonafluorobutoxy;
C1-C4-alkylthio and the alkylthio moieties of C1-C4-(alkylthio)carbonyloxy: for example methylthio, ethylthio, propylthio, 1-methylethylthio, butylthio, 1-methylpropylthio, 2-methylpropylthio and 1,1-dimethylethylthio;
C1-C4-haloalkylthio: a C1-C4-alkylthio radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, i.e., for example, fluoromethylthio, difluoromethylthio, trifluoromethylthio, chlorodifluoromethylthio, bromodifluoromethylthio, 2-fluoroethylthio, 2-chloroethylthio, 2-bromoethylthio, 2-iodoethylthio, 2,2-difluoroethylthio, 2,2,2-trifluoroethylthio, 2,2,2-trichloroethylthio, 2-chloro-2-fluoroethylthio, 2-chloro-2,2-difluoroethylthio, 2,2-dichloro-2-fluoroethylthio, pentafluoroethylthio, 2-fluoropropylthio, 3-fluoropropylthio, 2-chloropropylthio, 3-chloropropylthio, 2-bromopropylthio, 3-bromopropylthio, 2,2-difluoropropylthio, 2,3-difluoropropylthio, 2,3-dichloropropylthio, 3,3,3-trifluoropropylthio, 3,3,3-trichloropropylthio, 2,2,3,3,3-pentafluoropropylthio, heptafluoropropylthio, 1-(fluoromethyl)-2-fluoroethylthio, 1-(chloromethyl)-2-chloroethylthio, 1-(bromomethyl)-2-bromoethylthio, 4-fluorobutylthio, 4-chlorobutylthio, 4-bromobutylthio and nonafluorobutylthio;
C1-C4-alkylsulfonyl (C1-C4-alkyl-S(xe2x95x90O)2xe2x88x92), and the alkylsulfonyl moieties of C1-C4-alkylsulfonyloxy: for example methylsulfonyl, ethylsulfonyl, propylsulfonyl, 1-methylethylsulfonyl, butylsulfonyl, 1-methylpropylsulfonyl, 2-methylpropylsulfonyl and 1,1-dimethylethylsulfonyl;
C1-C6-alkylsulfonyl, and the alkylsulfonyl moieties of C1-C6-alkylsulfonyloxy: a C1-C4-alkylsulfonyl radical as mentioned above, and also, for example, pentylsulfonyl, 1-methylbutylsulfonyl, 2-methylbutylsulfonyl, 3-methylbutylsulfonyl, 1,1-dimethylpropylsulfonyl, 1,2-dimethylpropylsulfonyl, 2,2-dimethylpropylsulfonyl, 1-ethylpropylsulfonyl, hexylsulfonyl, 1-methylpentylsulfonyl, 2-methylpentylsulfonyl, 3-methylpentylsulfonyl, 4-methylpentylsulfonyl, 1,1-dimethylbutylsulfonyl, 1,2-dimethylbutylsulfonyl, 1,3-dimethylbutylsulfonyl, 2,2-dimethylbutylsulfonyl, 2,3-dimethylbutylsulfonyl, 3,3-dimethylbutylsulfonyl, 1-ethylbutylsulfonyl, 2-ethylbutylsulfonyl, 1,1,2-trimethylpropylsulfonyl, 1,2,2-trimethylpropylsulfonyl, 1-ethyl-1-methylpropylsulfonyl and 1-ethyl-2-methylpropylsulfonyl;
C1-C4-haloalkylsulfonyl: a C1-C4-alkylsulfonyl radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, i.e., for example, fluoromethylsulfonyl, difluoromethylsulfonyl, trifluoromethylsulfonyl, chlorodifluoromethylsulfonyl, bromodifluoromethylsulfonyl, 2-fluoroethylsulfonyl, 2-chloroethylsulfonyl, 2-bromoethylsulfonyl, 2-iodoethylsulfonyl, 2,2-difluoroethylsulfonyl, 2,2,2-trifluoroethylsulfonyl, 2-chloro-2-fluoroethylsulfonyl, 2-chloro-2,2-difluoroethylsulfonyl, 2,2-dichloro-2-fluoroethylsulfonyl, 2,2,2-trichloroethylsulfonyl, pentafluoroethylsulfonyl, 2-fluoropropylsulfonyl, 3-fluoropropylsulfonyl, 2-chloropropylsulfonyl, 3-chloropropylsulfonyl, 2-bromopropylsulfonyl, 3-bromopropylsulfonyl, 2,2-difluoropropylsulfonyl, 2,3-difluoropropylsulfonyl, 2,3-dichloropropylsulfonyl, 3,3,3-trifluoropropylsulfonyl, 3,3,3-trichloropropylsulfonyl, 2,2,3,3,3-pentafluoropropylsulfonyl, heptafluoropropylsulfonyl, 1-(fluoromethyl)-2-fluoroethylsulfonyl, 1-(chloromethyl)-2-chloroethylsulfonyl, 1-(bromomethyl)-2-bromoethylsulfonyl, 4-fluorobutylsulfonyl, 4-chlorobutylsulfonyl, 4-bromobutylsulfonyl and nonafluorobutylsulfonyl;
C3-C6-alkenyloxy: for example prop-1-en-1-yloxy, prop-2-en-1-yloxy, 1-methylethenyloxy, buten-1-yloxy, buten-2-yloxy, buten-3-yloxy, 1-methylprop-1-en-1-yloxy, 2-methylprop-1-en-1-yloxy, 1-methylprop-2-en-1-yloxy, 2-methylprop-2-en-1-yloxy, penten-1-yloxy, penten-2-yloxy, penten-3-yloxy, penten-4-yloxy, 1-methylbut-1-en-1-yloxy, 2-methylbut-1-en-1-yloxy, 3-methylbut-1-en-1-yloxy, 1-methylbut-2-en-1-yloxy, 2-methylbut-2-en-1-yloxy, 3-methylbut-2-en-1-yloxy, 1-methylbut-3-en-1-yloxy, 2-methylbut-3-en-1-yloxy, 3-methylbut-3-en-1-yloxy, 1,1-dimethylprop-2-en-1-yloxy, 1,2-dimethylprop-1-en-1-yloxy, 1,2-dimethylprop-2-en-1-yloxy, 1-ethylprop-1-en-2-yloxy, 1-ethylprop-2-en-1-yloxy, hex-1-en-1-yloxy, hex-2-en-1-yloxy, hex-3-en-1-yloxy, hex-4-en-1-yloxy, hex-5-en-1-yloxy, 1-methylpent-1-en-1-yloxy, 2-methylpent-1-en-1-yloxy, 3-methylpent-1-en-1-yloxy, 4-methylpent-1-en-1-yloxy, 1-methylpent-2-en-1-yloxy, 2-methylpent-2-en-1-yloxy, 3-methylpent-2-en-1-yloxy, 4-methylpent-2-en-1-yloxy, 1-methylpent-3-en-1-yloxy, 2-methylpent-3-en-1-yloxy, 3-methylpent-3-en-1-yloxy, 4-methylpent-3-en-1-yloxy, 1-methylpent-4-en-1-yloxy, 2-methylpent-4-en-1-yloxy, 3-methylpent-4-en-1-yloxy, 4-methylpent-4-en-1-yloxy, 1,1-dimethylbut-2-en-1-yloxy, 1,1-dimethylbut-3-en-1-yloxy, 1,2-dimethylbut-3-en-1-yloxy, 1,2-dimethylbut-2-en-1-yloxy, 1,2-dimethylbut-3-en-1-yloxy, 1,3-dimethylbut-3-en-1-yloxy, 1,3-dimethylbut-2-en-1-yloxy, 1,3-dimethylbut-3-en-1-yloxy, 2,2-dimethylbut-3-en-1-yloxy, 2,3-dimethylbut-3-en-1-yloxy, 2,3-dimethylbut-2-en-1-yloxy, 2,3-dimethylbut-3-en-1-yloxy, 3,3-dimethylbut-1-en-1-yloxy, 3,3-dimethylbut-2-en-1-yloxy, 1-ethylbut-1-en-1-yloxy, 1-ethylbut-2-en-1-yloxy, 1-ethylbut-3-en-1-yloxy, 2-ethylbut-1-en-1-yloxy, 2-ethylbut-2-en-1-yloxy, 2-ethylbut-3-en-1-yloxy, 1,1,2-trimethylprop-2-en-1-yloxy, 1-ethyl-1-methylprop-2-en-1-yloxy, 1-ethyl-2-methylprop-1-en-1-yloxy and 1-ethyl-2-methylprop-2-en-1-yloxy;
C3-C6-alkenyl: prop-1-en-1-yl, prop-2-en-1-yl, 1-methylethenyl, buten-1-yl, buten-2-yl, buten-3-yl, 1-methylprop-1-en-1-yl, 2-methylprop-1-en-1-yl, 1-methylprop-2-en-1-yl, 2-methylprop-2-en-1-yl, penten-1-yl, penten-2-yl, penten-3-yl, penten-4-yl, 1-methylbut-1-en-1-yl, 2-methylbut-1-en-1-yl, 3-methylbut-1-en-1-yl, 1-methylbut-2-en-1-yl, 2-methylbut-2-en-1-yl, 3-methylbut-2-en-1-yl, 1-methylbut-3-en-1-yl, 2-methylbut-3-en-1-yl, 3-methylbut-3-en-1-yl, 1,1-dimethylprop-2-en-1-yl, 1,2-dimethylprop-1-en-1-yl, 1,2-dimethylprop-2-en-1-yl, 1-ethylprop-1-en-2-yl, 1-ethylprop-2-en-1-yl, hex-1-en-1-yl, hex-2-en-1-yl, hex-3-en-1-yl, hex-4-en-1-yl, hex-5-en-1-yl, 1-methylpent-1-en-1-yl, 2-methylpent-1-en-1-yl, 3-methylpent-1-en-1-yl, 4-methylpent-1-en-1-yl, 1-methylpent-2-en-1-yl, 2-methylpent-2-en-1-yl, 3-methylpent-2-en-1-yl, 4-methylpent-2-en-1-yl, 1-methylpent-3-en-1-yl, 2-methylpent-3-en-1-yl, 3-methylpent-3-en-1-yl, 4-methylpent-3-en-1-yl, 1-methylpent-4-en-1-yl, 2-methylpent-4-en-1-yl, 3-methylpent-4-en-1-yl, 4-methylpent-4-en-1-yl, 1,1-dimethylbut-2-en-1-yl, 1,1-dimethylbut-3-en-1-yl, 1,2-dimethylbut-1-en-1-yl, 1,2-dimethylbut-2-en-1-yl, 1,2-dimethylbut-3-en-1-yl, 1,3-dimethylbut-1-en-1-yl, 1,3-dimethylbut-2-en-1-yl, 1,3-dimethylbut-3-en-1-yl, 2,2-dimethylbut-3-en-1-yl, 2,3-dimethylbut-1-en-1-yl, 2,3-dimethylbut-2-en-1-yl, 2,3-dimethylbut-3-en-1-yl, 3,3-dimethylbut-1-en-1-yl, 3,3-dimethylbut-2-en-1-yl, 1-ethylbut-1-en-1-yl, 1-ethylbut-2-en-1-yl, 1-ethylbut-3-en-1-yl, 2-ethylbut-1-en-1-yl, 2-ethylbut-2-en-1-yl, 2-ethylbut-3-en-1-yl, 1,1,2-trimethylprop-2-en-1-yl, 1-ethyl-1-methylprop-2-en-1-yl, 1-ethyl-2-methylprop-1-en-1-yl and 1-ethyl-2-methylprop-2-en-1-yl.
The phenyl rings are preferably unsubstituted or carry one to three halogen atoms and/or one nitro group, one cyano group, one or two methyl, trifluoromethyl, methoxy or trifluoromethoxy groups.
Emphasis is given to those compounds of the formula I where
R7 is hydroxyl, C1-C6-alkoxy, C3-C6-alkenyloxy, C1-C6-alkylsulfonyloxy, C1-C6-alkylcarbonyloxy, phenylsulfonyloxy or phenylcarbonyloxy, where the phenyl radical of the two last-mentioned substituents may be partially or fully halogenated and/or may carry one to three of the following groups: nitro, cyano, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy or C1-C4-haloalkoxy.
Preference is given to the 3-(heterocyclyl)benzoylpyrazole derivatives of the formula I where:
X is O;
R1 is nitro, halogen, C1-C4-alkoxy or C1-C4-alkylthio; particularly preferably nitro, halogen or C1-C4-alkoxy; with particular preference halogen, such as fluorine, chlorine or bromine, or C1-C4-alkoxy, such as methoxy or ethoxy; with very particular preference chlorine or methoxy;
R2,R3,R4,R5 are hydrogen, C1-C4-alkyl or C1-C4-haloalkyl; particularly preferably hydrogen, methyl, ethyl, propyl, 1-methylethyl, fluoromethyl or chloromethyl; with particular preference hydrogen, methyl, ethyl or chloromethyl;
R6 is C1-C4-alkylthio or C1-C4-alkylsulfonyl; particularly preferably methylthio, ethylthio or 1-methyl-1-ethylthio, methylsulfonyl, ethylsulfonyl, 1-methylethylsulfonyl or propylsulfonyl; with particular preference methylsulfonyl, ethylsulfonyl, 1-methylethylsulfonyl or propylsulfonyl;
R7 is hydroxyl, C1-C6-alkoxy, C3-C6-alkenyloxy, C1-C6-alkylsulfonyloxy, C1-C6-alkylcarbonyloxy, C1-C4-(alkylthio)carbonyloxy, phenylsulfonyloxy or phenylcarbonyloxy, where the phenyl radical of the two last-mentioned substituents may be partially or fully halogenated and/or may carry one to three of the following groups: nitro, cyano, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy or C1-C4-haloalkoxy; particularly preferably hydroxyl, C1-C4-alkoxy, C3-C6-alkenyloxy, C1-C4-alkylsulfonyloxy, C1-C4-alkylcarbonyloxy, phenylsulfonyloxy or phenylcarbonyloxy, where the phenyl radical of the two last-mentioned substituents may be partially or fully halogenated and/or may carry one to three of the following groups: nitro, cyano, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy or C1-C4-haloalkoxy;
R8,R9 are C1-C4-alkyl; particularly preferably methyl, ethyl, propyl, 1-methyl-1-ethyl, butyl, 1-methyl-1-propyl and 2-methyl-1-propyl;
R10 is hydrogen or C1-C4-alkyl; particularly preferably C1-C4-alkyl; with particular preference methyl, ethyl or propyl;
R11 is hydrogen or C1-C4-alkyl; particularly preferably hydrogen or methyl.
Particular preference is given to the 3-(heterocyclyl)benzoylpyrazole derivatives of the formula I where
X is O;
R1 is halogen or C1-C4-alkoxy; particularly preferably halogen, such as fluorine, chlorine or bromine, or methoxy or ethoxy; with particular preference chlorine or methoxy;
R6 is C1-C4-alkylsulfonyl; particularly preferably methylsulfonyl, ethylsulfonyl, 1-methyl-1-ethylsulfonyl or propylsulfonyl;
R7 is hydroxyl, C1-C6-alkylsulfonyloxy, C1-C6-alkylcarbonyloxy, phenylsulfonyloxy or phenylcarbonyloxy, where the phenyl radical of the two last-mentioned substituents may be partially or fully halogenated and/or may carry one to three of the following groups: nitro, cyano, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy or C1-C4-haloalkoxy; particularly preferably hydroxyl;
R8,R9 are C1-C4-alkyl;
R10 is hydrogen or C1-C4-alkyl.
Very particular preference is given to the 3-(heterocyclyl)benzoylpyrazole derivatives of the formula I where
R8 is C2-C4-alkyl, for example ethyl, 1-methyl-1-ethyl, propyl or butyl;
R9 is C1-C4-alkyl, for example methyl or ethyl;
R10 is hydrogen or C1-C4-alkyl, for example methyl or ethyl.
Very particular preference is also given to the 3-(heterocyclyl)benzoylpyrazole derivatives of the formula I where
R8 is methyl;
R9 is C1-C4-alkyl, for example methyl, ethyl, propyl or butyl;
R10 is C1-C4-alkyl, for example methyl or ethyl.
Very particular preference is also given to the 3-(heterocyclyl)benzoylpyrazole derivatives of the formula I where
R8,R9 are methyl;
R10 is hydrogen.
Preference is also given to the 3-(heterocyclyl)benzoylpyrazole derivatives of the formula I where:
X is O
R1 is nitro, halogen, C1-C4-alkoxy or C1-C4-alkylthio; particularly preferably nitro, halogen or C1-C4-alkoxy; with particular preference halogen, such as fluorine, chlorine or bromine, or C1-C4-alkoxy, such as methoxy or ethoxy; with very particular preference chlorine or methoxy;
R2,R3,R4,R5 are hydrogen, C1-C4-alkyl or C1-C4-haloalkyl; particularly preferably hydrogen, methyl, ethyl, propyl, 1-methyl-1-ethyl, chloromethyl or fluoromethyl; with particular preference hydrogen, methyl, ethyl or chloromethyl;
R6 is halogen, nitro, C1-C4-haloalkyl, C1-C4-alkoxy or C1-C4-haloalkoxy; particularly preferably halogen, such as chlorine or bromine, nitro, C1-C2-haloalkyl, such as difluoromethyl or trifluoromethyl, C1-C2-alkoxy or C1-C2-haloalkoxy, such as difluoromethoxy, chlorodifluoromethoxy or trifluoromethoxy;
R7 is hydroxyl, C1-C6-alkoxy, C3-C6-alkenyloxy, C1-C6-alkylsulfonyloxy, C1-C6-alkylcarbonyloxy, C1-C4-(alkylthio)carbonyloxy, phenylsulfonyloxy or phenylcarbonyloxy, where the phenyl radical of the two last-mentioned substituents may be partially or fully halogenated and/or may carry one to three of the following groups: nitro, cyano, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy or C1-C4-haloalkoxy; particularly preferably hydroxyl, C1-C4-alkoxy, C3-C6-alkenyloxy, C1-C4-alkylsulfonyloxy, C1-C4-alkylcarbonyloxy, phenylsulfonyloxy or phenylcarbonyloxy, where the phenyl radical of the two last-mentioned substituents may be partially or fully halogenated and/or may carry one to three of the following groups: nitro, cyano, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy or C1-C4-haloalkoxy;
R8,R9 are C1-C4-alkyl; particularly preferably methyl, ethyl, propyl, 1-methyl-1-ethyl, butyl, 1-methyl-1-propyl and 2-methyl-1-propyl;
R10 is hydrogen or C1-C4-alkyl; particularly preferably C1-C4-alkyl; with particular preference methyl, ethyl or propyl;
R11 is hydrogen or C1-C4-alkyl; particularly preferably hydrogen or methyl.
Particular preference is given to the 3-(heterocyclyl)benzoylpyrazole derivatives of the formula I where
X is O;
R1 is halogen or C1-C4-alkoxy; particularly preferably halogen, such as fluorine, chlorine or bromine, or methoxy or ethoxy; with particular preference chlorine or methoxy;
R6 is halogen, nitro, C1-C4-haloalkyl, C1-C4-alkoxy or C1-C4-haloalkoxy; particularly preferably halogen, such as chlorine or bromine, nitro, C1-C2-haloalkyl, such as difluoromethyl or trifluoromethyl, C1-C2-alkoxy or C1-C2-haloalkoxy, such as difluoromethoxy;
R7 is hydroxyl, C1-C6-alkylsulfonyloxy, C1-C6-alkylcarbonyloxy, phenylsulfonyloxy or phenylcarbonyloxy, where the phenyl radical of the two last-mentioned substituents may be partially or fully halogenated and/or may carry one to three of the following groups: nitro, cyano, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy or C1-C4-haloalkoxy; particularly preferably hydroxyl;
R8,R9 are C1-C4-alkyl;
R10 is hydrogen or C1-C4-alkyl.
Very particular preference is given to the 3-(heterocyclyl)benzoylpyrazole derivatives of the formula I where
R8 is C2C4-alkyl, for example ethyl, 1-methyl-1-ethyl, propyl or butyl;
R9 is C1-C4-alkyl, for example methyl or ethyl;
R10 is hydrogen or C1-C4-alkyl, for example methyl or ethyl.
Very particular preference is also given to the 3-(heterocyclyl)benzoylpyrazole derivatives of the formula I where
R8 is methyl;
R9 is C1-C4-alkyl, for example methyl, ethyl, propyl or butyl;
R10 is C1-C4-alkyl, for example methyl or ethyl.
Very particular preference is also given to the 3-(heterocyclyl)benzoylpyrazole derivatives of the formula I where
R8,R9 are methyl;
R10 is hydrogen.
Preference is also given to the 3-(heterocyclyl)-substituted benzoylpyrazoles [sic] of the formula I where:
X is N(C1-C6-alkyl); particularly preferably N-methyl, N-ethyl, N-(1-methyl-1-ethyl) or N-propyl;
R1 is nitro, halogen, C1-C4-alkoxy or C1-C4-alkylthio; particularly preferably nitro, halogen or C1-C4-alkoxy; with particular preference halogen, such as fluorine, chlorine or bromine, or C1-C4-alkoxy, such as methoxy or ethoxy; with very particular preference chlorine or methoxy;
R2,R3,R4,R5 are hydrogen, C1-C4-alkyl or C1-C4-haloalkyl; particularly preferably hydrogen, methyl, ethyl, propyl, 1-methyl-1-ethyl, fluoromethyl or chloromethyl; with particular preference hydrogen, methyl, ethyl or chloromethyl;
R6 is halogen, nitro, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, C1-C4-haloalkylthio, C1-C4-alkylsulfonyl or C1-C4-haloalkylsulfonyl; particularly preferably halogen, such as fluorine, chlorine or bromine, nitro, C1-C4-haloalkyl, such as difluoromethyl or trifluoromethyl, C1-C4-alkoxy, such as methoxy or ethoxy, C1-C4-haloalkoxy, such as difluoromethoxy, chlorodifluoromethoxy or trifluoromethoxy, C1-C4-alkylthio, such as methylthio or ethylthio, or C1-C4-alkylsulfonyl, such as methylsulfonyl, ethylsulfonyl, 1-methyl-1-ethylsulfonyl or propylsulfonyl;
R7 is hydroxyl, C1-C6-alkoxy, C3-C6-alkenyloxy, C1-C6-alkylsulfonyloxy, C1-C6-alkylcarbonyloxy, C1-C4-(alkylthio)carbonyloxy, phenylsulfonyloxy or phenylcarbonyloxy, where the phenyl radical of the two last-mentioned substituents may be partially or fully halogenated and/or may carry one to three of the following groups: nitro, cyano, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy or C1-C4-haloalkoxy; particularly preferably hydroxyl, C1-C4-alkoxy, C3-C6-alkenyloxy, C1-C4-alkylsulfonyloxy, C1-C4-alkylcarbonyloxy, phenylsulfonyloxy or phenylcarbonyloxy, where the phenyl radical of the two last-mentioned substituents may be partially or fully halogenated and/or may carry one to three of the following groups: nitro, cyano, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy or C1-C4-haloalkoxy;
R8,R9 are C1-C4-alkyl; particularly preferably methyl, ethyl, propyl, 1-methyl-1-ethyl, butyl, 1-methyl-1-propyl and 2-methyl-1-propyl;
R10 is hydrogen or C1-C4-alkyl; particularly preferably C1-C4-alkyl; with particular preference methyl, ethyl or propyl;
R11 is hydrogen or C1-C4-alkyl; particularly preferably hydrogen or methyl.
Particular preference is given to the 3-(heterocyclyl)benzoylpyrazole derivatives of the formula I where
R7 is hydroxyl, C1-C6-alkylsulfonyloxy, C1-C6-alkylcarbonyloxy, phenylsulfonyloxy or phenylcarbonyloxy, where the phenyl radical of the two last-mentioned substituents may be partially or fully halogenated and/or may carry one to three of the following groups: nitro, cyano, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy or C1-C4-haloalkoxy; particularly preferably hydroxyl.
Preference is likewise given to the 3-(heterocyclyl)benzoyl-pyrazole derivatives of the formula I where the variables are as defined below:
X is O;
R1 is halogen or C1-C4-alkoxy; particularly preferably fluorine, chlorine, bromine, methoxy or ethoxy; particularly preferably chlorine or methoxy;
R2,R3,R4,R5 are hydrogen;
R6 is C1-C4-alkylsulfonyl; particularly preferably methylsulfonyl;
R7 is hydroxyl, C1-C6-alkoxy, C1-C4-(alkylthio)carbonyloxy or phenylcarbonyloxy, where the phenyl radical may be partially or fully halogenated and/or may carry one to three of the following groups: nitro, cyano, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy or C1-C4-haloalkoxy; particularly preferably hydroxyl, C1-C6-alkoxy or phenylcarbonyloxy, where the phenyl radical may be partially or fully halogenated and/or may carry one to three of the following groups: nitro, cyano, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy or C1-C4-haloalkoxy;
R8,R9 are C1-C4-alkyl;
R10 is hydrogen or C1-C4-alkyl;
R11 is hydrogen.
Very particular preference is given to the compounds of the formula Ia1 (xe2x89xa1I where R1=Cl; R8,R9=CH3; R10,R11=H), in particular to the compounds Ia1.1 to Ia1.300 of Table 1, where the radical definitions X and R1 to R11 are of particular importance for the compounds according to the invention, not only in combination with one another, but in each case also on their own. 
Extraordinary preference is also given to the compounds of the formula Ia2, in particular to the compounds Ia2.1 to Ia2.300, which differ from the corresponding compounds Ia1.1 to Ia1.300 in that R11 is methyl. 
Extraordinary preference is also given to the compounds of the formula Ia3, in particular to the compounds Ia3.1 to Ia3.300, which differ from the compounds Ia1.1 to Ia1.300 in that R8 is ethyl. 
Extraordinary preference is also given to the compounds of the formula Ia4, in particular to the compounds Ia4.1 to Ia4.300, which differ from the compounds Ia1.1 to Ia1.300 in that R8 is ethyl and R11 is methyl. 
Extraordinary preference is also given to the compounds of the formula Ia5, in particular to the compounds Ia5.1 to Ia5.300, which differ from the compounds Ia1.1 to Ia1.300 in that R8 is 1-methyl-1-ethyl. 
Extraordinary preference is also given to the compounds of the formula Ia6, in particular to the compounds Ia6.1 to Ia6.300, which differ from the compounds Ia1.1 to Ia1.300 in that R8 is 1-methyl-1-ethyl and R11 is methyl. 
Extraordinary preference is also given to the compounds of the formula Ia7, in particular to the compounds Ia7.1 to Ia7.300, which differ from the compounds Ia1.1 to Ia1.300 in that R10 is methyl. 
Extraordinary preference is also given to the compounds of the formula Ia8, in particular to the compounds Ia8.1 to Ia8.300, which differ from the compounds Ia1.1 to Ia1.300 in that R10 is methyl and R11 is methyl. 
Extraordinary preference is also given to the compounds of the formula Ia9, in particular to the compounds Ia9.1 to Ia9.300, which differ from the compounds Ia1.1 to Ia1.300 in that R8 and R9 are 1-methyl-1-ethyl. 
Extraordinary preference is also given to the compounds of the formula Ia10, in particular to the compounds Ia10.1 to Ia10.300, which differ from the compounds Ia1.1 to Ia1.300 in that R8 and R9 are 1-methyl-1-ethyl and R11 is methyl. 
Extraordinary preference is also given to the compounds of the formula Ia11, in particular to the compounds Ia11.1 to Ia11.300, which differ from the compounds Ia1.1 to Ia1.300 in that R8 is ethyl and R10 is methyl. 
Extraordinary preference is also given to the compounds of the formula Ia12, in particular to the compounds Ia12.1 to Ia12.300, which differ from the corresponding compounds Ia1.1 to Ia1.300 in that R8 is ethyl and R10 and R11 are methyl. 
Extraordinary preference is also given to the compounds of the formula Ia13, in particular to the compounds Ia13.1 to Ia13.300, which differ from the compounds Ia1.1 to Ia1.300 in that R1 is methoxy. 
Extraordinary preference is also given to the compounds of the formula Ia14, in particular to the compounds Ia14.1 to Ia14.300, which differ from the corresponding compounds Ia1.1 to Ia1.300 in that R1 is methoxy and R11 is methyl. 
Extraordinary preference is also given to the compounds of the formula Ia15, in particular to the compounds Ia15.1 to Ia15.300, which differ from the compounds Ia1.1 to Ia1.300 in that R1 is methoxy and R8 is ethyl. 
Extraordinary preference is also given to the compounds of the formula Ia16, in particular to the compounds Ia16.1 to Ia16.300, which differ from the compounds Ia1.1 to Ia1.300 in R1 is methoxy, R8 is ethyl and R11 is methyl. 
Extraordinary preference is also given to the compounds of the formula Ia17, in particular to the compounds Ia17.1 to Ia17.300, which differ from the compounds Ia1.1 to Ia1.300 in that R1 is methoxy and R8 is 1-methyl-1-ethyl. 
Extraordinary preference is also given to the compounds of the formula Ia18, in particular to the compounds Ia18.1 to Ia18.300, which differ from the compounds Ia1.1 to Ia1.300 in that R1 is methoxy, R8 is 1-methyl-1-ethyl and R11 is methyl. 
Extraordinary preference is also given to the compounds of the formula Ia19, in particular to the compounds Ia19.1 to Ia19.300, which differ from the compounds Ia1.1 to Ia1.300 in that R1 is methoxy and R10 is methyl. 
Extraordinary preference is also given to the compounds of the formula Ia20, in particular to the compounds Ia20.1 to Ia20.300, which differ from the compounds Ia1.1 to Ia1.300 in that R1 is methoxy, R10 is methyl and R11 is methyl. 
Extraordinary preference is also given to the compounds of the formula Ia21, in particular to the compounds Ia21.1 to Ia21.300, which differ from the compounds Ia1.1 to Ia1.300 in that R1 is methoxy and R8 and R9 are 1-methyl-1-ethyl. 
Extraordinary preference is also given to the compounds of the formula Ia22, in particular to the compounds Ia22.1 to Ia22.300, which differ from the compounds Ia1.1 to Ia1.300 in that R1 is methoxy, R8 and R9 are 1-methyl-1-ethyl and R11 is methyl. 
Extraordinary preference is also given to the compounds of the formula Ia23, in particular to the compounds Ia23.1 to Ia23.300, which differ from the compounds Ia1.1 to Ia1.300 in that R1 is methoxy, R8 is ethyl and R10 is methyl. 
Extraordinary preference is also given to the compounds of the formula Ia24, in particular to the compounds Ia24.1 to Ia24.300, which differ from the compounds Ia1.1 to Ia1.300 in that R1 is methoxy, R8 is ethyl and R10 and R11 are methyl. 
The 3-(heterocyclyl)benzoylpyrazole derivatives of the formula I can be obtained by various routes, for example by the processes below.
Process A:
Reaction of pyrazoles of the formula II with an activated benzoic acid IIIxcex1 or a benzoic acid IIIxcex2, which is preferably activated in situ, to give the corresponding acylation product IV, followed by rearrangement, gives compounds of the formula I where R7=OH. 
L1 is a nucleophilically displaceable leaving group, such as halogen, for example bromine, chlorine, hetaryl, for example imidazolyl, pyridyl, carboxylate, for example acetate, trifluoroacetate etc.
The activated benzoic acid can be employed directly, such as in the case of the benzoyl halides, or be generated in situ, for example using dicyclohexylcarbodiimide, triphenylphosphine/azodicarboxylic ester, 2-pyridine disulfide/triphenylphosphine, carbonyldiimidazole, etc.
It may be advantageous to carry out the acylation reaction in the presence of a base. The reactants and the auxiliary base are advantageously employed in equimolar amounts here. A slight excess of auxiliary base, for example from 1.2 to 1.5 molar equivalents, based on II, may be advantageous in certain cases.
Suitable auxiliary bases are tertiary alkylamines, pyridine or alkali metal carbonates. Suitable for use as solvents are, for example, chlorinated hydrocarbons, such as methylene chloride, 1,2-dichloroethane, aromatic hydrocarbons, such as toluene, xylene, chlorobenzene, ethers, such as diethyl ether, methyl tert-butyl ether, dimethoxyethane, tetrahydrofuran, dioxane, polar aprotic solvents, such as acetonitrile, dimethylformamide, dimethyl sulfoxide, or esters, such as ethyl acetate, or mixtures of these.
If the activated carboxylic acid components used are benzoyl halides, it may be advantageous to cool the reaction mixture to 0-10xc2x0 C. when adding this reaction partner. The mixture is subsequently stirred at 20-100xc2x0 C., preferably at 25-50xc2x0 C., until the reaction has ended. Work-up is carried out in a customary manner, for example by pouring the reaction mixture into water and extracting the product of value. Solvents which are particularly suitable for this purpose are methylene chloride, diethyl ether, dimethoxyethane and ethyl acetate. The organic phase is dried and the solvent is removed, after which the crude ester can be employed for the rearrangement without any further purification.
The rearrangement of the esters to give the compounds of the formula I is advantageously carried out at 20-400xc2x0 C. in a solvent and in the presence of a base and, if appropriate, using a cyano compound as catalyst.
Suitable solvents are, for example, acetonitrile, methylene chloride, 1,2-dichloroethane, dioxane, ethyl acetate, dimethoxyethane, toluene or mixtures of these. Preferred solvents are acetonitrile and dioxane.
Suitable bases are tertiary amines, such as triethylamine or pyridine, or alkali metal carbonates, such as sodium carbonate or potassium carbonate, which are preferably employed in an equimolar amount or an up to four-fold excess, based on the ester. Preference is given to using triethylamine or alkali metal carbonates, preferably in twice the equimolar amount, based on the ester.
Suitable cyano compounds are inorganic cyanides, such as sodium cyanide and potassium cyanide, and organic cyano compounds, such as acetone cyanohydrin and trimethylsilyl cyanide. They are employed in an amount of from 1 to 50 mol percent, based on the ester. Preference is given to using acetone cyanohydrin or trimethylsilyl cyanide, for example in an amount of from 5 to 15, preferably 10, mol percent, based on the ester.
Work-up can be carried out in a manner known per se. The reaction mixture is, for example, acidified with dilute mineral acid, such as 5% strength hydrochloric acid or sulfuric acid, and extracted with an organic solvent, for example methylene chloride or ethyl acetate. The organic extract can be extracted with 5-10% strength alkali metal carbonate solution, for example sodium carbonate or potassium carbonate solution. The aqueous phase is acidified and the resulting precipitate is filtered off with suction and/or extracted with methylene chloride or ethyl acetate, and the mixture is dried and concentrated. (Examples of the preparation of esters of hydroxypyrazoles and for the rearrangement of the esters are given, for example, in EP-A 282 944 and U.S. Pat. No. 4,643,757).
However, it is also possible to generate the xe2x80x9cacylation productxe2x80x9d IV in situ by reacting a pyrazole of the formula II, or an alkali metal salt thereof, with a 3-(heterocyclyl)benzene derivative of the formula V in the presence of carbon monoxide, a catalyst and a base. 
L2 is a leaving group, such as halogen, for example chlorine, bromine or iodine, or sulfonate, such as mesylate or triflate; preference is given to bromine or triflate.
The xe2x80x9cacylation productxe2x80x9d IV proceeds to react, directly or indirectly, to give the 3-(heterocyclyl)benzoylpyrazole derivative of the formula I.
Suitable catalysts are palladium-ligand complexes in which the palladium is present in oxidation state 0, metallic palladium, which has optionally been absorbed on a carrier, and preferably palladium(II) salts. The reaction with palladium(II) salts and metallic palladium is preferably carried out in the presence of complex ligands.
An example of a suitable palladium(0)-ligand complex is tetrakis(triphenylphosphine)palladium.
Metallic palladium is preferably absorbed on an inert carrier such as, for example, activated carbon, silica, alumina, barium sulfate or calcium carbonate. The reaction is preferably carried out in the presence of complex ligands such as, for example, triphenylphosphine.
Examples of suitable palladium(II) salts are palladium acetate and palladium chloride. The presence of complex ligands such as, for example, triphenylphosphine is preferred.
Suitable complex ligands for the palladium-ligand complexes, or in whose presence the reaction is preferably carried out with metallic palladium or palladium(II) salts, are tertiary phosphines whose structure is represented by the following formulae: 
where z is 1 to 4 and the radicals Ra to Rg are C1-C6-alkyl, C3-C6-cycloalkyl, aryl-C1-C2-alkyl or, preferably, aryl. Aryl is, for example, naphthyl and unsubstituted or substituted phenyl such as, for example, 2-tolyl and, in particular, unsubstituted phenyl.
The complex palladium salts can be prepared in a manner known per se starting from commercially available palladium salts such as palladium chloride or palladium acetate and the appropriate phosphines such as, for example, triphenylphosphine or 1,2-bis(diphenylphosphino)ethane. Many of the complexed palladium salts are commercially available. Preferred palladium salts are [(R)(+)2,2xe2x80x2-bis(diphenylphosphino)-1,1xe2x80x2-binaphthyl]palladium(II) chloride, bis(triphenylphosphine)palladium(II) acetate and, in particular, bis(triphenylphosphine)palladium(II) chloride.
The palladium catalyst is usually employed in a concentration of from 0.05 to 5 mol %, and preferably 1-3 mol %.
Suitable bases are tertiary amines, such as, for example, N-methylpiperidine, ethyldiisopropylamine, 1,8-bisdimethylaminonaphthalene or, in particular, triethylamine. Also suitable are alkali metal carbonates, such as sodium carbonate or potassium carbonate. However, mixtures of potassium carbonate and triethylamine are also suitable.
In general, from 2 to 4 molar equivalents, in particular 2 molar equivalents, of the alkali metal carbonate, and from 1 to 4 molar equivalents, in particular 2 molar equivalents, of the tertiary amine are employed, based on the 3-(heterocylyl)benzene derivative of the formula V.
Suitable solvents are nitriles, such as benzonitrile and acetonitrile, amides, such as dimethylformamide, dimethylacetamide, tetra-C1-C4-alkylureas or N-methylpyrrolidone and, preferably, ethers, such as tetrahydrofuran and methyl tert-butyl ethers. Particular preference is given to ethers, such as 1,4-dioxane and dimethoxyethane.
Process B:
Compounds of the formula I where R7xe2x89xa0hydroxyl are obtained by reacting compounds of the formula I where R7=hydroxyl with alkylating agents, sulfonylating agents or acylating agents L3xe2x80x94R7a (VI). 
L3 is a nucleophilically displaceable leaving group, such as halogen, for example bromine or chlorine, acyloxy, for example acetyloxy, ethylcarbonyloxy, or alkylsulfonyloxy, for example methylsulfonyloxy or trifluoromethylsulfonyloxy.
R7a is C1-C6-alkyl, C3-C6-alkenyl, C1-C6-alkylsulfonyl, C1-C6-alkylcarbonyl, C1-C6-(alkylthio)carbonyl, phenylsulfonyl or phenylcarbonyl, where the phenyl radical of the two last-mentioned substituents may be partially or fully halogenated and/or may carry one to three of the following groups: nitro, cyano, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy or C1-C4-haloalkoxy.
The compounds of the formula VI can be employed directly, such as, for example, in the case of the sulfonyl halides or sulfonic anhydrides, or be generated in situ, for example activated sulfonic acids (using sulfonic acid and dicyclohexylcarbonyldiimide, carbonyldiimidazole, etc.).
The starting materials are generally employed in equimolar amounts. However, it may also be advantageous to employ an excess of one component or the other.
If appropriate, it may be advantageous to carry out the reaction in the presence of a base. The reactants and the auxiliary base are advantageously employed in equimolar amounts here. An excess of auxiliary base, for example from 1.5 to 3 molar equivalents, based on I, may be advantageous in certain cases.
Suitable auxiliary bases are tertiary alkylamines, such as triethylamine, pyridine, alkali metal carbonates, for example sodium carbonate or potassium carbonate, and alkali metal hydrides, for example sodium hydride. Preference is given to using triethylamine and pyridine.
Suitable solvents are, for example, chlorinated hydrocarbons, such as methylene chloride and 1,2-dichloroethane, aromatic hydrocarbons, for example toluene, xylene, chlorobenzene, ethers, such as diethyl ether, methyl tert-butyl ether, tetrahydrofuran and dioxane, polar aprotic solvents, such as acetonitrile, dimethylformamide, dimethyl sulfoxide, or esters, such as ethyl acetate, or mixtures of these.
In general, the reaction temperature is in the range from 0xc2x0 C. to the boiling point of the reaction mixture.
Work-up can be carried out in a manner known per se to give the product.
The pyrazoles of the formula II used as starting materials are known or can be prepared by processes known per se (for example EP-A 240 001 and J. Prakt. Chem. 315, 383 (1973)).
The activated benzoic acids IIIxcex1 can be obtained in a manner known per se from the benzoic acids IIIxcex2. The latter for their part are obtained by hydrolysis from the corresponding esters VII. These can be prepared by converting an oxime or hydrazone of the formula VIII into the corresponding hydroxyamic acid halide, in particular hydroxamic acid chloride, or carbohydrazide halide, in particular carbohydrazide chloride; generating a nitrile oxide or nitrileimine in situ and reacting this with an alkene (cf. for example Chem. Ber. 106, 3258-3274 (1973). 
However, the benzoic acids IIIxcex2 can also be obtained by converting an oxime or hydrazone of the formula IX into the corresponding nitrile oxides or nitrileimines and reacting these with alkenes to give the corresponding cycloaddition products (cf., for example, Chem. Ber. 106, 3252-3274 (1973)). Thus, for example, the oxime of the formula IX (X=O) is oxidized with sodium hypochlorite and reacted with a suitable alkene in an inert solvent such as methylene chloride, chloroform, tetrahydrofuran, dioxane or acetonitrile. The product is then, in the presence of a catalyst and a base, converted into the benzoic acid IIIxcex2 using carbon monoxide and water. 
L2 is a leaving group, such as halogen, for example chlorine, bromine or iodine, or sulfonate, such as mesylate or triflate; preference is given to bromine or triflate.
With respect to the carbonylation reaction, what has been said above applies analogously.